U.S. patent number 8,420,763 [Application Number 12/911,890] was granted by the patent office on 2013-04-16 for fluorooxyalkylene group-containing polymer composition, a surface treatment agent comprising the same and an article treated with the agent.
This patent grant is currently assigned to Shin-Etsu Chemical Co., Ltd.. The grantee listed for this patent is Hirofumi Kishita, Noriyuki Koike, Koichi Yamaguchi, Yuji Yamane. Invention is credited to Hirofumi Kishita, Noriyuki Koike, Koichi Yamaguchi, Yuji Yamane.
United States Patent |
8,420,763 |
Yamane , et al. |
April 16, 2013 |
Fluorooxyalkylene group-containing polymer composition, a surface
treatment agent comprising the same and an article treated with the
agent
Abstract
An object of the present invention is to provide a
fluorooxyalkylene group-containing polymer composition, which
yields a coating having excellent adhesior to a substrate, good
water- and oil-repellency, a low dynamic friction coefficient, good
releasing property, good abrasion resistance and good stain
resistance, and to provide a surface treatment agent comprising the
same. The present inventors have found that a composition
comprising a fluorooxyalkylene group-containing polymer having a
fluorinated group and a hydrolyzable group at each terminal and a
fluorooxyalkylene group-containing polymer having hydrolyzable
groups at both terminals can form a coating which has excellent
water- and oil-repellency, a low dynamic friction coefficient, good
releasing property, good abrasion resistance, and good stain
resistance.
Inventors: |
Yamane; Yuji (Annaka,
JP), Koike; Noriyuki (Takasaki, JP),
Kishita; Hirofumi (Annaka, JP), Yamaguchi; Koichi
(Takasaki, JP) |
Applicant: |
Name |
City |
State |
Country |
Type |
Yamane; Yuji
Koike; Noriyuki
Kishita; Hirofumi
Yamaguchi; Koichi |
Annaka
Takasaki
Annaka
Takasaki |
N/A
N/A
N/A
N/A |
JP
JP
JP
JP |
|
|
Assignee: |
Shin-Etsu Chemical Co., Ltd.
(Tokyo, JP)
|
Family
ID: |
43301868 |
Appl.
No.: |
12/911,890 |
Filed: |
October 26, 2010 |
Prior Publication Data
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|
|
|
Document
Identifier |
Publication Date |
|
US 20110098402 A1 |
Apr 28, 2011 |
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Foreign Application Priority Data
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Oct 27, 2009 [JP] |
|
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2009-247032 |
Oct 4, 2010 [JP] |
|
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2010-225128 |
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Current U.S.
Class: |
528/42 |
Current CPC
Class: |
C09D
171/02 (20130101); G02B 1/105 (20130101); C08G
65/336 (20130101); G02B 1/14 (20150115); C09D
5/165 (20130101); C08G 65/007 (20130101); C08L
71/02 (20130101); C08L 71/02 (20130101); C08L
2666/22 (20130101); C09D 171/02 (20130101); C08L
2666/22 (20130101); G02B 27/0006 (20130101); C08G
2650/48 (20130101) |
Current International
Class: |
C08G
77/24 (20060101) |
Field of
Search: |
;528/42 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
|
|
|
|
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|
1 300 433 |
|
Apr 2003 |
|
EP |
|
58-167597 |
|
Oct 1983 |
|
JP |
|
2000-143991 |
|
May 2000 |
|
JP |
|
2003-238577 |
|
Aug 2003 |
|
JP |
|
2007-297589 |
|
Nov 2007 |
|
JP |
|
WO 2008/027698 |
|
Mar 2008 |
|
WO |
|
WO 2008/121469 |
|
Oct 2008 |
|
WO |
|
Other References
European Search Report dated Dec. 15, 2010, issued in European
Patent Application No. 10 18 8316. cited by applicant.
|
Primary Examiner: Moore; Margaret
Attorney, Agent or Firm: Birch, Stewart, Kolasch &
Birch, LLP
Claims
The invention claimed is:
1. A fluorooxyalkylene group-containing polymer composition
comprising a fluorooxyalkylene group-containing polymer having a
hydrolyzable group at one terminal and a fluorooxyalkylene
group-containing polymer having hydrolyzable groups at both
terminals wherein the fluorooxyalkylene group-containing polymers
are represented by the following formula (1): A-Rf.sup.1-B (1)
wherein Rf.sup.1 is a divalent linear fluorooxyalkylene group
having 5 to 100 repeating units represented by
--C.sub.dF.sub.2dO--, wherein d is, independently of each other, an
integer of from 1 to 6; and A and B are, independently of each
other, an Rf.sup.2 group, wherein Rf.sup.2 is selected from the
group consisting of F, H and a monovalent fluorinated group having
a CF.sub.3 or CF.sub.2H group at the terminal, or a group
represented by the following formula (2) ##STR00019## wherein Q is
a divalent organic group, Z is a divalent to septivalent
organopolysiloxane group having a siloxane bond, which is a linear
or cyclic organopolysiloxane moiety having 2 to 5 silicon atoms, R
is an alkyl group having 1 to 4 carbon atoms or a phenyl group, X
is a hydrolyzable group, a is 2 or 3, and b is an integer of from 1
to 6, c is an integer of from 1 to 5, and .beta. is 1; wherein the
terminal Rf.sup.2 group accounts for 30 to 75 mole %, relative to a
total of all of the terminal groups in the composition.
2. The fluorooxyalkylene group-containing polymer composition
according to claim 1, wherein the composition comprises 40 to 90
mole % of the fluorooxyalkylene group-containing polymer having a
hydrolyzable group at one terminal, and 10 to 60 mole % of the
fluorooxyalkylene group-containing polymer having hydrolyzable
groups at both terminals.
3. The fluorooxyalkylene group-containing polymer composition
according to any one of claims 1 and 2, wherein Rf.sup.1 is a
divalent linear fluorooxyalkylene group represented by the
following formula (5);
--CF.sub.2(OC.sub.2F.sub.4).sub.f(OCF.sub.2).sub.gOCF.sub.2-- (5)
wherein f is an integer of from 0 to 80, g is an integer of from 1
to 80, and a total of f and g is from 5 to 100, and these repeating
units may be sequenced at random.
4. The fluorooxyalkylene group-containing polymer composition
according to claim 1, wherein Q is a hydrocarbon group having 2 to
12 carbon atoms and may have one or more bond selected from the
group consisting of an amide bond, an ether bond, an ester bond and
a vinyl bond.
5. The fluorooxyalkylene group-containing polymer composition
according to claim 1, wherein X is a group selected from the group
consisting of alkoxy groups, oxyalkoxy groups, acyloxy groups,
alkenyloxy groups and halogen atoms.
6. A surface treatment agent comprising a fluorooxyalkylene
group-containing polymer composition comprising a fluorooxyalkylene
group-containing polymer having a hydrolyzable group at one
terminal and a fluorooxyalkylene group-containing polymer having
hydrolyzable groups at both terminals wherein the fluorooxyalkylene
group-containing polymers are represented by the following formula
(1): A-Rf.sup.1-B (1) wherein Rf.sup.1 is a divalent linear
fluorooxyalkylene group having 5 to 100 repeating units represented
by --C.sub.dF.sub.2dO--, wherein d is, independently of each other,
an integer of from 1 to 6; and A and B are, independently of each
other, an Rf.sup.2 group, wherein Rf.sup.2 is selected from the
group consisting of F, H and a monovalent fluorinated group having
a CF.sub.3 or CF.sub.2H group at the terminal, or a group
represented by the following formula (2) ##STR00020## wherein Q is
a divalent organic group, Z is a divalent to septivalent
organopolysiloxane group having a siloxane bond, which is a linear
or cyclic organopolysiloxane moiety having 2 to 5 silicon atoms, R
is an alkyl group having 1 to 4 carbon atoms or a phenyl group, X
is a hydrolyzable group, a is 2 or 3, and b is an integer of from 1
to 6, c is an integer of from 1 to 5, and .beta. is 1; wherein the
terminal Rf.sup.2 group accounts for 30 to 75 mole %, relative to a
total of all of the terminal groups in the composition, and/or a
condensate of a hydrolyzate obtained by partially hydrolyzing the
polymer composition.
7. An article treated with the surface treatment agent according to
claim 6.
8. An optical article treated with the surface treatment agent
according to claim 6.
Description
CROSS REFERENCE
This application claims the benefits of Japanese Patent application
No. 2009-247032 filed on Oct. 27, 2009, and Japanese Patent
application No. 2010-225128 filed on Oct. 4, 2010 the contents of
which are hereby incorporated by reference.
FIELD OF THE INVENTION
The present invention relates to a fluorooxyalkylene
group-containing polymer composition, specifically, relates to a
composition which forms a coating having good adhesiveness to a
substrate, water- and oil-repellency, a low dynamic friction
coefficient, a good releasing property, good abrasion resistance
and good stain resistance, and relates to a surface treatment agent
comprising the same.
BACKGROUND OF THE INVENTION
Compounds containing a perfluorooxyalkylene moiety generally have a
very small surface free energy and, accordingly, have good water-
and oil-repellency, chemical resistance, lubricity, releasing
property, and antifouling property. Taking advantage of these
properties, they are widely used as, for example, water- and
oil-repellent agents or antifouling agents for paper or fiber,
lubricants for magnetic storage media, oil repellents components
for precision apparatuses, releasing agents, cosmetic, and
protective coatings.
These properties, on the other hand, mean that such compounds do
not stick or closely adhere to other materials, either. Even if
they can be applied to a material, it is difficult to have a
coating closely adhered to the material.
Meanwhile, silane coupling agents are well known as an agent which
bonds an organic compound to a surface of a substrate such as glass
or a cloth. The silane coupling agents have an organic functional
group and a reactive silyl group, usually an alkoxy silyl group, in
a molecule. The alkoxy silyl group autocondenses in the presence of
moisture in air to become a siloxane and forms a coating. At the
same time, the alkoxy silyl group chemically and physically bonds
to a surface of glass or metal to form a durable coating. Taking
advantage of these properties, the silane coupling agents are
widely used as a coating agent for various substrates. Compounds
based on the silane coupling agents to provide the feature of the
perfluorooxyalkylene moieties on a surface of a substrate are
known.
For instance, Japanese Patent Application Laid-Open No.
Sho-58-167597 discloses that a fluoroaminosilane compound
represented by the following formula is applied on glass to attain
high water- and oil-repellency:
##STR00001##
wherein R.sup.2 and R.sup.3 are alkyl groups having 1 to 4 carbon
atoms, R.sup.1 is CH.sub.2CH.sub.2CH.sub.2 or
CH.sub.2CH.sub.2NHCH.sub.2CH.sub.2CH.sub.2, h is an integer of from
0 to 8, and "i" is 2 or 3.
However, the perfluorooxyalkylene moiety of this compound is
relatively short, so that the characteristics of the
perfluorooxyalkylene moiety, particularly lubricity, a releasing
property, and an antifouling property, are not well exhibited.
Japanese Patent Application Laid-Open No. 2000-143991 discloses
perfluoropolyether-modified aminosilane represented by the
following formula, as a compound having a long perfluorooxyalkylene
moiety,
##STR00002##
wherein X is a hydrolyzable group, R.sup.4 is a monovalent
hydrocarbon group, R.sup.6 is a hydrogen atom or a monovalent
hydrocarbon group, R.sup.5 is an alkylene group optionally
interrupted by an NH group, j is an integer of from 14 to 49, and k
is 2 or 3.
The perfluoropolyether-modified aminosilane has a high water- and
oil-repellency on account of the terminal fluorine-containing
group. However, its stain resistance and lubricity are insufficient
due to the branch structure in the main chain.
Recently, there is an increasing need for technology to attain
fingerprint proofness or easy removal of fouling on a surface of a
display for better appearance or visibility. Thus, a material which
meets these requirements is desired.
Japanese Patent Application Laid-Open No. 2003-238577 discloses a
perfluoropolyether-modified silane represented by the following
formula, as a treatment agent which has a perfluorooxyalkylene
moiety with no branch structure in the main chain,
##STR00003##
wherein Rf is a divalent linear perfluoropolyether group, R is an
alkyl group having 1 to 4 carbon atoms or a phenyl group, X is a
hydrolyzable group, 1 is an integer of from 0 to 2, m is an integer
of from 1 to 5, and a is 2 or 3.
Lenses and anti-reflection films treated with the aforesaid
perfluoropolyether-modified silane are good in stainproofness, easy
removal of fouling, lubricity and a releasing property, compared to
the perfluoropolyether-modified silane having a branch structure.
Further, abrasion resistance is superior to the prior
perfluoropolyether-modified silane, because the both terminals
thereof are fixed on a substrate. However, the lubricity intrinsic
to this perfluoropolyether is not well exhibited due to the both
terminals being fixed on a substrate, so that further improvement
is required. Further, unreacted terminal moieties remaining after
curing reduce water- and oil-repellency, releasing property and
lubricity. Therefore, improvement on these properties by decreasing
unreacted terminal moiety is desired.
Japanese Patent Application Laid-Open No. 2007-297589 discloses a
perfluoropolyether-modified silane represented by the following
formula, as a treatment agent which has improved lubricity,
(Z.sup.2Q).sub..beta.Rf(QZ.sup.1A.sub..alpha.).sub.2-.beta.
wherein Rf is a divalent perfluoroether-containing group, Q is a
divalent organic group, Z.sup.1 and Z.sup.2 are organopolysiloxane
moieties, A is a monovalent group having a terminal reactive silyl
group, .alpha. is an integer of from 1 to 8, and .beta. is the
number larger than 0 and less than 2.
However, this compound does not have a terminal fluorinated group,
so that its water- and oil-repellency, dynamic friction coefficient
and releasing property are inferior.
Patent literature 1: Japanese Patent Application Laid-Open No.
Sho-58-167597
Patent literature 2: Japanese Patent Application Laid-Open No.
2000-143991
Patent literature 3: Japanese Patent Application Laid-Open No.
2003-238577
Patent literature 4: Japanese Patent Application Laid-Open No.
2007-297589
SUMMARY OF THE INVENTION
Problems to be Solved by the Invention
Stain resistance depends on a dynamic friction on a surface of a
coating, if releasing properties of stains are same. Therefore, a
surface treatment agent is desired which attains good water- and
oil-repellency, low dynamic friction coefficient, and good
releasing property all together. Further, of two coatings which
have same adhesiveness to a substrate, a coating having a lower
dynamic friction has better attrition resistance and abrasion
resistance, compared to another coating having a higher dynamic
friction, and thereby maintains stain resistance for a longer
period.
An object of the present invention is to provide a
fluorooxyalkylene group-containing polymer composition, which
yields a coating having excellent adhesior to a substrate, good
water- and oil-repellency, a low dynamic friction coefficient, good
releasing property, good abrasion resistance and good stain
resistance, and to provide a surface treatment agent comprising the
same.
Means to Solve the Problems
The present inventors have found that a composition comprising a
fluorooxyalkylene group-containing polymer having a fluorinated
group and a hydrolyzable group at each terminal and a
fluorooxyalkylene group-containing polymer having hydrolyzable
groups at both terminals can form a coating which has excellent
water- and oil-repellency, a low dynamic friction coefficient, good
releasing property, good abrasion resistance, and good stain
resistance.
Thus, the present invention provides a fluorooxyalkylene
group-containing polymer composition comprising a fluorooxyalkylene
group-containing polymer having a hydrolyzable group at one
terminal and a fluorooxyalkylene group-containing polymer having
hydrolyzable groups at both terminals
wherein the fluorooxyalkylene group-containing polymers are
represented by the following formula (1): A-Rf.sup.1-B (1)
wherein Rf.sup.1 is a divalent liner fluorooxyalkylene group having
5 to 100 repeating units represented by --C.sub.dF.sub.2dO--,
wherein d is, independently of each other, an integer of from 1 to
6; and A and B are, independently of each other, an Rf.sup.2 group
or a group represented by the following formula (2), wherein
Rf.sup.2 is selected from the group consisting of F, H and a
monovalent fluorinated group having a CF.sub.3 or CF.sub.2H group
at the terminal,
##STR00004##
wherein Q is a divalent organic group, Z is a divalent to
septivalent organopolysiloxane group having a siloxane bond, R is
an alkyl group having 1 to 4 carbon atoms or a phenyl group, X is a
hydrolyzable group, a is 2 or 3, and b is an integer of from 1 to
6, c is an integer of from 1 to 5, and .beta. is 0 or 1;
wherein of the Rf.sup.2 group accounts for 30 to 75 mole %,
relative to a total of all of the terminal groups in the
composition, and provides a surface treatment agent comprising the
same and an article treated with the agent.
Effects of the Invention
A coating obtained from the present fluorooxyalkylene
group-containing polymer composition can adhere strongly to a
substrate via the hydrolyzable silyl group. The present
fluorooxyalkylene group-containing polymer composition comprises a
polymer which has a hydrolyzable group at the one terminal,
hereinafter called "a one-terminal modified polymer", and a polymer
which has hydrolyzable groups at the both terminals, hereinafter
called "a both-terminal modified polymer". A degree of steric
freedom of the one-terminal modified polymer is larger than that of
the both-terminal modified polymer, and contributes to lubricity of
the surface. The one-terminal modified polymer can provide a good
adhesiveness by itself. Further the both-terminal modified polymer
gives the coating increased adhesion to a substrate in all around
the coating. The fluorine atoms in the polymer tend to orient
toward a surface of the coating to provide better water- and
oil-repellency and releasing property.
The present fluorooxyalkylene group-containing polymer composition
can provide a coating which has excellent water- and
oil-repellency, low dynamic friction coefficient, good releasing
property, good abrasion resistance and stain resistance. Therefore,
the present composition can be used for a long period for various
coating applications.
BRIEF DESCRIPTION ON THE DRAWINGS
FIG. 1 is a chart of .sup.1H-NMR spectra of the compound 1.
FIG. 2 is a chart of .sup.1H-NMR spectra of the compound 2.
BEST MODES OF THE INVENTION
In the afore-mentioned formula (1), Rf.sup.1 is a divalent
fluorooxyalkylene group. This group may be linear in view of a low
dynamic friction coefficient. Preferably, the fluorooxyalkylene
group has 5 to 100, preferably 10 to 80, more preferably 15 to 60,
repeating units represented by --C.sub.dF.sub.2dO--, wherein d is,
independently of each other, an integer of from 1 to 6, preferably
1 to 4.
For the aforesaid repeating unit represented by the formula
--C.sub.dF.sub.2dO--, mention may be made of the following units.
Rf.sup.1 may comprise a single kind of unit or a combination of two
or more kinds of units. --CF.sub.2O-- --CF.sub.2CF.sub.2O--
--CF.sub.2CF.sub.2CF.sub.2O-- --CF.sub.2CF.sub.2CF.sub.2CF.sub.2O--
--CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2O--
--CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2O--
Preferably, Rf.sup.1 which comprises aforesaid repeating units is
selected from the groups represented by the following formula (3)
or (4):
--C.sub.eF.sub.2e(CF.sub.2CF.sub.2CF.sub.2O).sub.pC.sub.eF.sub.2e--
(3)
wherein p is an integer of from 5 to 100 and e is an integer of
from 1 to 3,
--C.sub.eF.sub.2e(OC.sub.2F.sub.4).sub.f(OCF.sub.2).sub.gOCF.sub.2--
(4)
wherein f is an integer of from 0 to 80, g is an integer of from 0
to 80, a total of f and g is from 5 to 100, and e is an integer of
from 1 to 3, and these repeating units may be sequenced at random.
Preferably, a total of f and g is 10 to 80, more preferably 15 to
60. If the total of f and g is larger than the aforesaid upper
limit, the adhesiveness and the curability may be poor. If the
total of f and g is less than the aforesaid lower limit, the
properties of the fluorooxyalkylene group cannot be provided
sufficiently.
Among these, preferred is a group represented by the following
formula (5) in view of a low dynamic friction coefficient:
--CF.sub.2(OC.sub.2F.sub.4).sub.f(OCF.sub.2).sub.gOCF.sub.2--
(5)
wherein f is an integer of from 0 to 80, g is an integer of from 1
to 80, and f+g is an integer of from 5 to 100, and these repeating
units may be sequenced at random.
In the afore-mentioned formula (1), A and B are, independently of
each other, the Rf.sup.2 group or a group represented by the
following formula (2):
##STR00005## wherein Rf.sup.2 is selected from F, H and a
monovalent fluorinated group having a CF.sub.3 or CF.sub.2H group
at the terminal, and preferably a perfluoro group.
In the afore-mentioned formula (2), X is, independently of each
other, a hydrolyzable group. Examples of X include alkoxy groups
having 1 to 10 carbon atoms such as methoxy, ethoxy, propoxy and
butoxy groups; oxyalkoxy groups having 2 to 10 carbon atoms such as
methoxymethoxy and methoxyethoxy groups; acyloxy groups having 1 to
10 carbon atoms such as an acetoxy group; alkenyloxy groups having
2 to 10 carbon atoms such as an isopropenoxy group; and halogen
atoms such as chlorine, bromine, and iodine atoms. Among these,
methoxy, ethoxy, iropropenoxy groups and a chlorine atom are
preferred.
R is an alkyl group having 1 to 4 carbon atoms such as methyl and
ethyl groups, and a phenyl group. Among these, preferred is a
methyl group. "a" is 2 or 3, preferably 3 in view of reactivity and
adhesiveness to a substrate. "b" is an integer of from 1 to 6,
preferably 1 to 3, and c is an integer of from 1 to 5, preferably 1
to 3.
In the afore-mentioned formula (2), Q is a linking group to connect
Rf.sup.1 with Z.sup.1, or Rf.sup.1 with the (CH.sub.2).sub.c group.
Preferred is a hydrocarbon group having 2 to 12 carbon atoms which
may have one or more bonds selected from an amide bond, an ether
bond, an ester bond and a vinyl bond. Examples of Q include the
following:
##STR00006##
In the afore-mentioned formula (2), Z is a divalent to septivalent
organopolysiloxane moiety having a siloxane bond. Z is preferably a
liner or cyclic organopolysiloxane moiety having 2 to 13 silicon
atoms, preferably 2 to 5 silicon atoms. Z may contain a silalkylene
structure where two silicon atoms are bonded via an alkylene group,
that is, Si--(CH.sub.2).sub.n--Si. The present fluorooxyalkylene
group-containing polymer composition has siloxane bonds in the
molecule, so that the present composition can become a coating
which has excellent attrition resistance and abrasion
resistance.
Preferably, the organopolysiloxane moiety has an alkyl group having
1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, or a phenyl
group. The alkylene group in the silalkylene bond preferably has 2
to 6 carbon atoms, more preferably 2 to 4 carbon atoms. Examples of
Z include the following;
##STR00007## ##STR00008##
The fluorooxyalkylene group-containing polymer composition having a
CF.sub.3 group at the terminal can be prepared by the following
process.
First, a terminal of a perfluorooxy compound having carboxylic
functions at the both terminals is partially fluorinated to obtain
the following mixture of polymers. A conversion to the terminal
CF.sub.3 group can be controlled by adjusting the amount of the
fluorine gas supplied to control the fluorination. Polymers having
carboxylic functions may be adsorbed on an acid adsorbent to be
separated, and a ratio of the one-terminal modified polymer and the
both-terminal modified polymer can be determined according to
.sup.19F-NMR and .sup.1H-NMR analysis.
##STR00009##
wherein Rf is a divalent fluorooxyalkylene group, preferably having
5 to 100, more preferably 10 to 80, further preferably 15 to 60,
repeating units represented by C.sub.dF.sub.2d0, wherein d is,
independently of each other, an integer of from 1 to 6, and
preferably 1 to 4.
A substituted or unsubstituted hydrocarbon group having 3 to 17
carbon atoms and an unsaturated group at a terminal is bonded to
the terminal carboxylic functions in the afore-described polymers
via an amide bond, an ether bond, an ester bond or a vinyl bond.
The introduction may be carried out according to any conventional
method. For instance, a fluorooxyalkylene group-containing polymer
where the Rf.sup.1 group is bonded to the (CH.sub.2).sub.c group,
wherein c is 1, via --CH.sub.2OCH.sub.2CH.sub.2-- group can be
prepared in the following process. First, the terminal carboxylic
function remaining in the polymer mixture is reduced with sodium
bis(2-methoxyethoxy)aluminum hydride or in a catalytic
hydrogenation to obtain the following mixture of polymers,
F.sub.3C-Rf-CF.sub.2CH.sub.2OH
HOH.sub.2CCF.sub.2-Rf-CF.sub.2CH.sub.2OH F.sub.3C-Rf-CF.sub.3
wherein Rf is as defined above,
Then, a compound having an unsaturated terminal radical is reacted
with in the terminal hydroxyl group of the perfluorooxyalkylene
group-containing polymer according to a conventional method. For
example, the afore-mentioned polymer mixture is reacted with
brominated ally in the presence of tetrabutylammonium hydrogen
sulfate, to which sodium hydroxide solution is then added dropwise
to make it alkaline to thereby obtain the following mixture of
polymers, F.sub.3C-Rf-CF.sub.2CH.sub.2OCH.sub.2CH.dbd.CH.sub.2
H.sub.2C.dbd.CHCH.sub.2OCH.sub.2CF.sub.2-Rf-CF.sub.2CH.sub.2OCH.sub.2CH.d-
bd.CH.sub.2 F.sub.3C-Rf-CF.sub.3
wherein Rf is as defined above.
Subsequently, a hydrolyzable silyl group is introduced at the
unsaturated terminal radical of the polymers. This is done by an
addition reaction of the terminal unsaturated radical-containing
polymers prepared from the afore-described process with an
organosilicon compound having an SiH bond at one terminal and a
hydrolyzable group at the other terminal. The hydrolyzable group is
as described for X above. Examples of the organosilicon compound
include a terminal alkoxy group-containing organohydrogensilane.
For instance, in a case where the unsaturated terminal
radical-containing polymers are reacted with trimethoxysilane,
i.e., HSi(OCH.sub.3).sub.3, a mixture of polymers as described
below is obtained. The addition reaction can be carried out in the
presence of an addition reaction catalyst, such as a platinum
compound, according to any conventional method.
CF.sub.3Rf-CF.sub.2CH.sub.2OC.sub.3H.sub.6Si(OCH.sub.3).sub.3
(CH.sub.3O).sub.3SiC.sub.3H.sub.6OCH.sub.2CF.sub.2-Rf-CF.sub.2CH.sub.2OC.-
sub.3H.sub.6Si(OCH.sub.3).sub.3 CF.sub.3-Rf-CF.sub.3
wherein Rf is as defined above.
Alternatively, the unsaturated terminal radical-containing polymers
may be reacted with an organosilicon compound having SiH bonds, for
instance 2 to 8 SiH groups. After the end of the reaction, there
are many remaining SiH bonds in a molecule of the polymers.
Therefore, the remaining SiH groups are reacted with an
organosilicon compound having an unsaturated radical and a
hydrolyzable group to increase the number of a terminal
hydrolyzable group.
Alternatively, the unsaturated terminal radical-containing polymers
are reacted with an alkoxysilane compound having an SiH bond at a
terminal, such as a 1:1 adduct of tetramethyldisiloxane (HM) with
vinyltrimethoxysilane (VMS) to obtain the following mixture of
polymers. The addition reaction can be carried out in the presence
of an addition reaction catalyst, such as a platinum compound,
according to any conventional method.
##STR00010##
wherein Rf is as defined above,
Alternatively, the fluorooxyalkylene group-containing polymers
which have the --CF.sub.2H group at the terminal can be prepared by
the following process. First, terminal carboxyl groups at both
terminals of the flyorooxyalkyrene-containing polymer are converted
to hydroxyl groups by reduction with sodium
bis(2-methoxyethoxy)aluminum hydride or by catalytic hydrogenation
with a noble metal catalyst to obtain the following mixture of
polymers. A desired conversion to the terminal hydroxyl groups can
be obtained by adjusting the amount of sodium
bis(2-methoxyethoxy)aluminum hydride supplied or the like.
HOOCCF.sub.2-Rf-CF.sub.2CH.sub.2OH
HOH.sub.2CCF.sub.2-Rf-CF.sub.2CH.sub.2OH
HOOCCF.sub.2-Rf-CF.sub.2COOH
wherein Rf is as defined above,
The hydroxyl groups of the aforesaid mixture is reacted with
brominated ally in the presence of tetrabutylammonium hydrogen
sulfate, and then the mixture is made alkaline to convert the
terminal hydroxyl groups into allyl ether groups; and CF.sub.2COOH
groups into CF.sub.2H groups, resulting in the following mixture of
polymers, HF.sub.2C-Rf-CF.sub.2CH.sub.2OCH.sub.2CH.dbd.CH.sub.2
H.sub.2C.dbd.CHCH.sub.2OCH.sub.2CF.sub.2-Rf-CF.sub.2CH.sub.2OCH.sub.2CH.d-
bd.CH.sub.2 HF.sub.2C-Rf-CF.sub.2H
wherein Rf is as defined above,
Subsequently, the aforesaid fluorooxyalkylene group-containing
polymers are reacted with a 1:1 adduct of tetramethyldisiloxane
(HM) with vinyltrimethoxysilane (VMS) in the presence of a platinum
compound to obtain the following mixture of polymers. The addition
reaction can be carried out according to any conventional method,
preferably in the presence of an addition reaction catalyst, such
as a platinum compound,
##STR00011##
wherein Rf is as defined above.
In the present fluorooxyalkylene group-containing polymer
composition has the terminal Rf.sup.2 group accounts preferably for
30 to 75 mole %, more preferably 40 to 70 mole %, relative to a
total moles of all of the terminal groups. If the mole percentage
exceeds the aforesaid upper limit, the number of the hydrolyzable
groups which can react with a substrate is small, so that the
adhesiveness is poor. If the mole percentage is less than the
aforesaid lower limit, the properties of the both-terminal modified
polymer is dominating, so that a low dynamic friction coefficient,
good releasing property, and high water- and oil-repellency cannot
be obtained.
The present fluorooxyalkylene group-containing polymer composition
preferably comprises 40 to 90 mole %, more preferably 55 to 85 mole
%, of the one-terminal modified polymer, and 10 to 60 mole %, more
preferably 15 to 45 mole %, of the both-terminal modified polymer.
If the amount of the one-terminal modified polymer is too large,
the number of the hydrolyzable groups which can react with a
substrate is too small, so that the adhesiveness is poor. If the
amount of the both-terminal modified polymer is too large, the
properties of the both-terminal modified polymer are dominating, so
that low dynamic friction coefficient, good releasing property, and
high water- and oil-repellency cannot be obtained.
The present fluorooxyalkylene group-containing polymer composition
may further comprise a fluorooxyalkylene group-containing polymer
whose terminals are not functionalized. The amount of the
non-functionalized fluorooxyalkylene group-containing polymer is
preferably 13 to 125 mole %, more preferably 18 to 95 mole %,
relative to the total mole of the one-terminal modified polymer and
the both-terminal modified polymer.
The present invention provides a surface treatment agent comprising
the aforesaid fluorooxyalkylene group-containing polymer
composition as an active ingredient. The composition may contain a
condensate of a hydrolyzate which can be obtained by subjecting a
part of the terminal hydrolyzable group(s) of the fluorooxyalkylene
group-containing polymer composition to hydrolysis, which is then
condensation reacted in a conventional manner.
The surface treatment agent may contain a catalyst for hydrolysis
and condensation reactions. Examples of the catalyst include
organic tin compounds such as bibutyltin dimethoxide and dibutyltin
dilaurate; organic titanium compounds such as tetra-n-butyl
titanate; organic acids such as acetic acid, methanesulfonic acid
and fluorinated carboxylic acid; and inorganic acids such as
hydrochloric acid and sulfuric acid. Among these, preferred are
acetic acid, tetra-n-butyl titanate, dibutyltin dilaurate and
fluorinated carboxylic acid. A content of the catalyst may be a
catalytic amount, which ranges typically from 0.01 to 5 parts by
weight, particularly from 0.1 to 1 part by weight, per 100 parts by
weight of the fluorooxyalkylene group-containing polymer and/or the
condensate of a hydrolyzate obtained by partially hydrolyzing the
polymer composition.
The surface treatment agent may contain a solvent. Examples of the
solvent include fluorinated aliphatic hydrocarbon solvents such as
perfluoroheptane and perfluoroctane; fluorinated aromatic
hydrocarbon solvents such as m-xylenehexafluoride, bezotrifluoride
and 1,3-Bis(trifluoromethyl)benzene; fluorinated ether solvents
such as methyl perfluorobutyl ether, ethyl perfluorobutyl ether,
and perfluoro(2-butyltetrahydrofuran); fluorinated alkylamine
solvents such as perfluorotributylamine and
perfluorotripentylamine; hydrocarbon solvents such as petroleum
benzene, mineral spirits, toluene, and xylene; ketone solvents such
as acetone, methylethylketone, and methylisobutylketone. Among
these, fluorinated solvents are preferred in view of solubility and
wettability of the composition. Particularly preferred are
m-xylenehexafluoride, perfluoro(2-butyltetrahydrofuran),
perfluorotributylamine and ethyl perfluorobutyl ether.
A mixture of two or more of the aforesaid solvents may be used.
Preferably, the fluorooxyalkylene group-containing polymer and the
condensate of the hydrolyzate obtained by partially hydrolyzing the
polymer composition are dissolved homogeneously. An optimum
concentration of the fluorooxyalkylene group-containing polymer
composition in a solvent may be decided, depending on treatment
conditions, and is preferably from 0.01 to 10 wt %, particularly
from 0.05 to 5 wt %.
The surface treatment agent may be applied to a substrate by any
known methods, such as brushing, dipping, spraying and vapor
deposition. The composition may be cured at a temperature selected
depending on a curing method. When the composition is applied by
brushing or dipping, a cured temperature is preferably from room
temperature to 80 degrees C. The curing is carried out preferably
in a humid environment to promote the curing reaction. A thickness
of a cured coating may be selected depending on the type of a
substrate, and is typically from 0.1 nm to 100 nm, particularly
from 1 to 20 nm.
A substrate to be treated with the present surface treatment agent
may be various substrates, such as paper, cloths, metals and metal
oxides, glass, plastics, ceramics and quartz, but is not limited to
these. The present composition can provide water- and
oil-repellency, releasing property, low dynamic friction
coefficient or stain resistance to these substrates.
Examples of an article to be treated and treatment with the present
surface treatment agent include the following: coating for
preventing fingerprints or sebum from adhering to optical articles
such as car navigation equipments, mobile phones, digital cameras,
digital camcorders, PDAs', portable audio players, car audio
devices, game machines, lenses of spectacles, lenses of cameras,
filters for lenses, dark glasses, medical devices such as gastric
cameras, copy machines, personal computers, liquid crystal
displays, organic EL displays, plasma displays, touch panel
displays, protection films, and anti-reflection films;
water-repellent and stainproof coatings for sanitary products such
as bathtubs and washbasins; stainproof coatings for window glass of
automobiles, trains and airplanes, and head lamp covers; water
repellent and stainproof coatings for building materials for
exterior wall; grease buildup-preventing coatings for kitchen
building materials; water repellent, stainproof, bill-, poster- and
graffiti-preventing coatings for telephone booths; coatings for
water repellency and fingerprint prevention on artworks; coatings
for preventing fingerprint on compact discs and DVDs'; release
agents for nanoimprint molds; and for modifying flowability and
dispersibility of paint additives, resin modifying agents, and
inorganic fillers, or improving a lubrication property of tapes and
films.
EXAMPLES
The present invention will be explained in detail by reference to
the Examples and the Comparative Examples, but shall not be limited
thereto.
The mixture of polymers represented by the following formulas (6a),
(6b) or (6c) was prepared by partially fluorinating the
perfluorooxy compound having carboxylic function at both terminals,
C4000 from Solvay Solexis Inc., with a fluorine gas. The polymers
having a carboxylic function(s) were adsorbed to an acid adsorbent
and separated to determining a ratio of the polymers according to
.sup.19F-NMR analysis.
F.sub.3C(OC.sub.2F.sub.4).sub.p(OCF.sub.2).sub.q--OCF.sub.2COOH
(6a)
HOOC--CF.sub.2--(OC.sub.2F.sub.4).sub.p(OCF.sub.2).sub.q--OCF.sub.2COOH
(6b) F.sub.3C(OC.sub.2F.sub.4).sub.p(OCF.sub.2).sub.q--OCF.sub.3
(6c) (p/q=0.9, the average of p+q was 45)
Example 1
In a reactor, placed were and dissolved 50 g of the aforesaid
mixture consisting of 52 mole % of (6a), 24 mole % of (6b) and 24
mole % of (6c), wherein the molar ratio of the terminal CF.sub.3
group was 50 mole %, relative to the total moles of the terminal
groups in the mixture, and a mixed solvent of g of
1,3-Bis(trifluoromethyl)benzene and 10 g of tetrahydrofuran. 30
Grams of a 40% solution of sodium bis (2-methoxyethoxy) aluminum
hydride in toluene was added dropwise into the mixture and stirred
at room temperature for 3 hours, to which appropriate amount of
hydrochloric acid was added, and sufficiently stirred, and then
washed with water. The lower phase was taken out and the solvent
was distilled off to obtain 40 g of a liquid product. According to
.sup.19F-NMR analysis, the product obtained was a mixture of the
compounds represented by the following formulas (7a), (7b) and
(7c), and the molar ratio of the terminal CF.sub.3 group was 50
mole %, relative to the total moles of the terminal groups.
F.sub.3C(OC.sub.2F.sub.4).sub.p(OCF.sub.2).sub.q--OCF.sub.2CH.sub.2OH
(7a)
HOH.sub.2C--CF.sub.2--(OC.sub.2F.sub.4).sub.p(OCF.sub.2).sub.q--OCF.-
sub.2CH.sub.2OH (7b)
F.sub.3C(OC.sub.2F.sub.4).sub.p(OCF.sub.2).sub.q--OCF.sub.3 (7c)
(p/q=0.9, the average of p+q was 45)
In a reactor, 40 g of the aforesaid mixture of the compounds of
(7a), (7b) and (7c), 3.5 g of brominated ally and 0.4 g of
tetrabutylammonium hydrogen sulfate were placed and stirred at 50
degrees C. for 3 hours. 5.2 Grams of an aqueous 30% sodium
hydroxide solution was added dropwise and aged at 55 degrees C. for
12 hours. Then, an appropriate amount of fluorinated solvent, PF
5060 from 3M Ltd., and hydrochloric acid were added and stirred,
and then washed with water. The lower phase was taken out and the
solvent was distilled off to obtain 30 g of a liquid product.
According to .sup.19F-NMR and .sup.1H-NMR analysis, the product
obtained was a mixture of the compounds represented by the
following formulas (8a), (8b) and (8c), and the molar ratio of the
terminal CF.sub.3 group was 50 mole %, relative to the total moles
of the terminal groups.
F.sub.3C(OC.sub.2F.sub.4).sub.p(OCF.sub.2).sub.q--OCF.sub.2CH.sub.2OCH.su-
b.2CH.dbd.CH.sub.2 (8a)
H.sub.2C.dbd.CHCH.sub.2OCH.sub.2--CF.sub.2--(OC.sub.2F.sub.4).sub.p(OCF.s-
ub.2).sub.q--OCF.sub.2CH.sub.2OCH.sub.2CH.dbd.CH.sub.2 (8b)
F.sub.3C(OC.sub.2F.sub.4).sub.p(OCF.sub.2).sub.q--OCF.sub.3 (8c)
(p/q=0.9, the average of p+q was 45)
Subsequently, in a reactor, 30 g of the aforesaid mixture of the
compounds of (8a), (8b) and (8c), 20 g of
1,3-Bis(trifluoromethyl)benzene and 3 g of hydrosilyl-containing
alkoxysilane, 03 MS from Shinetsu chemical Co., Ltd., 0.10 g of a
solution of a chloroplatinic acid/vinyl siloxane complex in toluene
(containing 2.5.times.10.sup.-8 mole of Pt) were placed and aged at
70 degrees C. for 1 week. Then, the solvent and unreacted compounds
were distilled off under reduced pressure to obtain 29.8 g of a
liquid product.
The .sup.1H-NMR chart of the product obtained is shown in FIG. 1.
The chemical shifts in .sup.1H-NMR (reference: TMS, ppm) are as
shown below.
--CH.sub.2CH.sub.2Si.ident. 0.50.about.0.72 ppm, 1.61.about.1.72
ppm
SiOCH.sub.3 3.41.about.3.66 ppm
--CH.sub.2OCH.sub.2-- 3.41.about.3.83 ppm
The molar ratio of the terminal CF.sub.3 group was 50 mole %,
relative to the total moles of the terminal groups. The product
obtained was the mixture of 52 mole % of (9a), 24 mole % of (9b)
and 24 mole % of (9c) (hereinafter, referred to as Composition 1).
F.sub.3C(OC.sub.2F.sub.4).sub.p(OCF.sub.2).sub.q--OCF.sub.2CH.sub.2OC.sub-
.3H.sub.6Si(OCH.sub.3).sub.3 (9a)
(CH.sub.3O).sub.3SiC.sub.3H.sub.6OCH.sub.2--CF.sub.2--(OC.sub.2F.sub.4).s-
ub.p(OCF.sub.2).sub.q--OCF.sub.2CH.sub.2OC.sub.3H.sub.6Si(OCH.sub.3).sub.3
(9b) F.sub.3C(OC.sub.2F.sub.4).sub.p(OCF.sub.2).sub.q--OCF.sub.3
(9c) (p/q=0.9, the average of p+q was 45)
Example 2
In a reactor, 30 g of the aforesaid mixture of the compounds of
(8a), (8b) and (8c) were dissolved in 20 g of
1,3-Bis(trifluoromethyl)benzene, to which 0.10 g of a solution of a
chloroplatinic acid/vinyl siloxane complex in toluene (containing
2.5.times.10.sup.-8 mole of Pt) and 2.5 g of a 1:1 adduct (HM-VMS)
of tetramethyldisiloxane (HM) with vinyltrimethoxysilane (VMS) were
added dropwise, and then aged at 90 degrees C. for 2 hours. Then,
the solvent and unreacted compounds were distilled off under
reduced pressure to obtain 31.5 g of a liquid product.
The aforesaid HM-VMS was prepared in the following process.
In a reactor, 40 g of tetramethyldisiloxane (HM) and 40 g of
toluene were placed and heated to 80 degrees C., to which a mixture
of 44.2 g of vinyltrimethoxysilane (VMS) and 2 g of a solution of a
chloroplatinic acid/vinyl siloxane complex in toluene (containing
1.1.times.10.sup.-7 mole of Pt) was added dropwise slowly. Then,
the resulting mixture was purified by distillation to obtain 84 g
of an adduct (HM-VMS) represented by the following formula.
##STR00012##
The .sup.1H-NMR chart of the product obtained in Example 2 is shown
in FIG. 2. The chemical shifts in .sup.1H-NMR (reference: TMS, ppm)
are as shown below. It is noted that, a peak around 2.4 ppm
indicates toluene which was added in the determination, and does
not relate to the obtained product.
##STR00013##
The molar ratio of the terminal CF.sub.3 group was 50 mole %,
relative to the total moles of the terminal groups. The obtained
product was a mixture of 52 mole % of (10a), 24 mole % of (10b) and
24 mole % of (10c) (hereinafter, referred to as Composition 2).
##STR00014## (p/q=0.9, the average of p+q was 45)
Examples 3-7
The procedures in Example 1 were repeated to prepare compositions 3
to 7, except that the molar ratio of the terminal CF.sub.3 group
was 30 mole %, 40 mole %, 60 mole %, 70 mole % or 75 mole %,
respectively.
Preparation of Surface Treatment Agents and Cured Coatings
The perfluorooxyalkylene group-containing polymer compositions
obtained in Examples 1 to 7 were dissolved in
1,3-Bis(trifluoromethyl)benzene in a 20 wt % concentration to
obtain surface treatment agents 1 to 7. 10 Milligrams of each
surface treatment agent was vacuum deposited on each six glass
slides, at a pressure of 3.8.times.10.sup.-3 Pa and a temperature
of 740 degrees C., and left at 40 degrees C. and an 80% humidity
for 24 hours to form a cured coating. The three glass slides
obtained were immediately washed by pouring a fluorinated solvent,
AK 225 from Asahi Glass Co., Ltd., and a contact angle and a
dynamic friction coefficient were determined, followed by a peeling
test. Further, the remaining three glass slides were subjected to
an abrasion resistant test.
Surface treatment agents and cured coatings of Comparative Examples
1 and 2 were prepared and evaluated by repeating the procedures of
Example 2, except that the molar ratio of the terminal CF.sub.3
group was 25 mole % or 85 mole %. Surface treatment agents and
cured coatings of Comparative Examples 3 to 8 were prepared and
evaluated by repeating the procedures in Examples 1 to 7, except
that the compounds or compositions indicated below were used.
Comparative Example 3
(CH.sub.3O).sub.3SiC.sub.3H.sub.6OCH.sub.2--CF.sub.2(OC.sub.2F.sub.4).su-
b.p(OCF.sub.2).sub.q--OCF.sub.2--CH.sub.2OC.sub.3H.sub.6Si(OCH.sub.3).sub.-
3 (p/q=0.9, the average of p+q was 45)
Comparative Example 4
The composition of 50 mole % of (11a), 25 mole % of (11b) and 25
mole % of (11c).
##STR00015## (p/q=0.9, the average of p+q was 45)
Comparative Example 5
##STR00016## (p/q=0.9, the average of p+q was 45)
Comparative Example 6
##STR00017##
Comparative Example 7
##STR00018##
Comparative Example 8
CF.sub.3(OC.sub.2F.sub.4).sub.p(OCF.sub.2).sub.q--OCF.sub.3
(p/q=0.9, the average of p+q was 45)
The cured coatings obtained were evaluated in the following
method.
Evaluation of Water- and Oil-Repellency
Using a contact angle meter, prop Master from Kyowa Interface
Science Co., Ltd., a water contact angle and an oleic acid contact
angle of the cured coatings were measured.
Dynamic Friction Coefficient
The dynamic friction coefficient against Bemcot from Asahi Kasei
was measured in the following conditions with a surface property
test machine, 14FW from Shinto Scientific Co., Ltd.
Contact area: 35 mm.times.35 mm
Load: 200 g
Evaluation of Releasing Property
The releasing property was measured in the following conditions
with an autograph, AG-IS from Shimadzu Co., Ltd. Treatment with an
adhesive (an adhesive tape was sticked to a test piece): Nitto No.
31 B, 19 mm in width Bonding pressure: load of 20 g/cm.sup.2 Aging:
25 degrees C./24 hours Peeling speed: 300 mm/minute, angle of 180
degrees Evaluation of a Property of Wipping Off Marking Ink
A surface of the cured coating was painted with a permanent marker,
High Macky from Zebra Co., Ltd. Then, the marking ink was wiped off
with tissue paper, Ellemoi from Kamishoji Co., Ltd. The surface
after wiped off was visually observed to evaluate on the following
criteria:
+++: all of the marking ink was wiped off easily at one time,
++: a little marking ink remained after one time wipping,
+: almost a half of the marking ink remained after one time
wipping, and
-: the marking ink could not be wiped off at all.
Scrub Resistance
Using a rubbing tester from Shinto Scientific Co., Ltd., the cured
coating was scrubbed under the following conditions, and then the
water repellency and the marking ink-wiping off property were
evaluated. Test environment: 25 degrees C., relative humidity of
40% Scrubbing material: A steel wool, BONSTAR #0000, fixed on a tip
(1 cm.sup.2) of a tester which top contacts with the cured coating
Scrub distance (one way): 30 mm Scrub speed: 1800 mm/min Load: 1 kg
Number of scrubbing times: 400 times
The results are as seen in Table 1.
TABLE-US-00001 TABLE 1 water oil dynamic releasing property of
repellency repellency friction property, wipping off (.degree.)
(.degree.) coefficient N/18 mm marking ink Example 1 114 73 0.05
0.05 +++ Example 2 116 73 0.05 0.05 +++ Example 3 111 71 0.07 0.05
+++ Example 4 112 71 0.06 0.05 +++ Example 5 115 73 0.05 0.04 +++
Example 6 116 74 0.04 0.04 +++ Example 7 112 72 0.07 0.08 +++
Comparative Example 1 109 69 0.07 0.10 +++ Comparative Example 2 90
63 0.25 0.33 + Comparative Example 3 110 70 0.10 0.12 +++
Comparative Example 4 107 66 0.07 0.12 +++ Comparative Example 5
110 68 0.10 0.12 +++ Comparative Example 6 115 74 0.24 0.15 +++
Comparative Example 7 115 75 0.23 0.35 +++ Comparative Example 8 56
60 0.34 0.40 +
The perfluorooxyalkylene group-containing polymer compositions of
Examples 1 to 7 had the high water- and oil-repellency and the low
dynamic friction coefficients. The compounds of Comparative
Examples 3 and 5 were a perfluorooxyalkylene group-containing
polymer having hydrolyzable groups at the both terminals. The both
terminals of the molecule were fixed to the substrate, so that the
dynamic friction coefficients were high, the water- and
oil-repellency and releasing property were inferior to those of the
Examples. The composition of Comparative Example 4 did not have a
terminal fluorine group, so that the water- and oil-repellency and
releasing property were inferior to those of the Examples. The
polymer of Comparative Example 8 did not have a hydrolyzable group
and could not bond to the substrate, so that the polymer could not
be fixed on the substrate and the desired surface property could
not be obtained. The compound of Comparative Examples 6 and 7
having a branched structure in the perfluorooxyalkylene chain had a
high kinetic viscosity, so that the dynamic friction coefficient
was high and the releasing property was inferior to those of the
Examples.
The results of the scrub resistance test are as seen in Table
2.
TABLE-US-00002 TABLE 2 water marking ink-wiping repellency after
off property scrubbed (.degree.) after scrubbed Example 1 105 +++
Example 2 105 +++ Example 3 100 ++ Example 4 102 ++ Example 5 107
+++ Example 6 102 ++ Example 7 100 ++ Comparative Example 1 91 -
Comparative Example 2 76 - Comparative Example 3 85 - Comparative
Example 4 92 - Comparative Example 5 85 - Comparative Example 6 54
- Comparative Example 7 65 - Comparative Example 8 49 -
As seen in Table 2, the perfluorooxyalkylene group-containing
polymer of Examples 1 to 7 could maintain the property of the
coating after scrubbed with the steel wool. However, the cured
coatings of Comparative Examples 1 to 8 were peeled off easily.
INDUSTRIAL APPLICABILITY
The fluoropolyoxyalkylene group-containing polymer composition of
the present invention can provide a coating which has excellent
water- and oil-repellency, low dynamic friction coefficient, good
releasing property, and abrasion resistance. Therefore, the present
composition can be used in various coating applications for a long
period of time. Additionally, the coating has excellent stain
resistance, so that the present composition can be used suitably
for a coating for lenses of spectacles, anti-reflection films,
polarization plates, television sets, touch panel displays, mobile
phones, accessories and precision molds.
* * * * *